DE3301024A1 - METHOD FOR THE PRODUCTION OF STABLE SOLUTIONS OF CATIONIC METHINE DYES AND THEIR USE FOR SPINNING - Google Patents

Description

BAYER AKTIENGESELLSCHAFT 5090 Leverkusen, Bayerwerk

Central area 4 β Μ 83

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Process for the preparation of stable solutions of cationic methine dyes and their use for Spin dyeing

For spin dyeing of acid modified synthetic fibers, for example of acid modified polyamide and Polyester fibers and polyacrylonitrile fibers, suitable Solutions of cationic methine dyes were previously made by dissolving the finished dyes in one with the Solvent compatible with the spinning system. the Premd salts from manufacturing must be carefully removed as they clog the spinneret system. In particular, chlorides can lead to corrosion problems.

It has now been found that ready-to-use spinning solutions of cationic methine dyes are free of mineral salts obtained when their preparation by condensation of aromatic-isocyclic or -heterocyclic or araliphatic aldehydes and methylene or amino group-containing compounds in one for spin dyeing

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suitable organic solvent in the presence of a produces free sulfonic or phosphonic acid.

Suitable organic solvents are preferably the amides of lower aliphatic carboxylic acids, in particular Dimethyl and diethyl formamide and dimethylacetamide.

According to the new process, solutions of dyes of the general formula are preferably used

A - CH = CH - (N- ^ jJ B R.

(D

wherein

for 0 or 1,

for an isocyclic or heterocyclic aromatic Radical or a radical of the formula

for alkyl, alkenyl or aralkyl,

B for an isocyclic or heterocyclic aromatic Radical or a radical of the formula

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* I »

n * t »·

R for hydrogen, alkyl or aralkyl or for alkylene, which is connected to B in the o-position to the nitrogen,

X for an anion of the formula

Y SO ₃ ⁽ ' or PO ₂

γ

and

Y is alkyl, aryl or alkoxy

stand in which A or B bears a positive charge, and in which a, A, B, R, R ₁ , R ₂ and Y can be substituted by nonionic radicals,

by condensation of aldehydes of the formula

A-CHO (II)

with compounds of the formula CH ₃

^R 1

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V * ψ

or by condensation of aldehydes of the formula

CH.

1
with amines of the formula

(IV) "^ CH-CHO

R,

NH-B (V)

wor in

A, B, a, R and R _{1 have} the meaning given in formula (I) _f

in the presence of acids of the formula

Y SO ₃ H (VI) or

PO ₂ H (VII)

in which

Y has the meaning given above, prepared in an organic solvent.

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-JEs-

As acids are to be mentioned in particular those of the formula (VI) and (VII), in which

Y stands for an alkoxy radical with 1-4 C atoms, a phenyl radical optionally substituted by 1-3 alkyl radicals with 1-4 C atoms, alkoxy radicals with 1-4 C atoms, halogen or hydroxyl, or a C ..- to C ₄ -Alkyl radical.

Acids of the formula (VI) are very particularly preferred in which

Y is methyl, phenyl or p-tolyl.

Preferred group of dyes which can be prepared by the new process correspond to the general ones Formulas

= CH-N- ^ B

R-

(R ⁴ ).

YSO.

(VIII)

-n;

YSO.

(IX)

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- Jq -

and

worm

R "

YSO

(χ)

for hydrogen, an alkyl radical with 1 to 4 carbon atoms, halogen, alkoxy with 1 to 4 carbon atoms, phenoxy, benzyloxy, benzyl, carboxyl, phenoxyethyl, phenoxyethoxy, an alkyl carboxylate with 1 to 4 carbon atoms, one optionally by 1 or 2 C ₁ to C 1 -C alkyl radicals substituted carbonamide group, a sulfonamide group optionally substituted by 1 or 2 C 1 -C 4 alkyl radicals, alkylsulphonyl with 1 to 4 C atoms, phenylsulphonyl, cyano, trifluoromethyl, acetyl - or benzoyl group,

for one optionally by hydroxy, alkoxy, acyloxy, halogen, cyano, carboxy, Cj-C ^ carbalkoxy, Carbonamido or acetyl substituted alkyl radical with 1 to 4 carbon atoms,

has the same meaning as R or, together with the benzene ring B, a tetralin, naphthalene or Benzdioxanrxngsystem forms,

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• β »

R stands for hydrogen or a radical with the same meaning as R,

7 6

R can have the same meaning as R, or optionally by alkyl or alkoxy with 1 to 4 carbon atoms substituted phenyl, or an alkyl substituent which has a 5- or 6-membered Ring to the adjacent position of the aryl ring B closes, this being formed heterocyclic 5- or 6-membered ring optionally alkyl-substituted or with or with a further carbocyclic ring can be condensed,

R ⁸ for hydrogen, C ₁ to C ₄ alkyl,

R represents hydrogen, C ₁ to C-alkyl, phenyl optionally substituted by alkyl having 1 to 4 carbon atoms,

y has the meaning given above and η and ρ stand for 1 or 2.

Of the dyes of the formulas (VIII), (IX) and (X), mention should be made in particular of those in which

η and ρ stand for 1,

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R for hydrogen, chlorine, methyl, methoxy, ethoxy, benzyl, phenoxy, benzyloxy or carbomethoxy,

R ³ for methyl,

4th
R for hydrogen, methyl, methoxy, ethoxy, benzyl, benzyloxy, phenoxy, chlorine, C ₁ - to C ^ -alkyl-substituted carbonamide or together with the ring B for a naphthalene, tetrahydronaphthalene or benz dioxane ring system,

R is hydrogen or preferably an alkyl radical which closes a 5- or 6-ring to the o-position of ring B, which _{can be substituted by 1 to 3 C 1} - to C ₂ -alkyl groups or condensed with a cyclohexane ring,

R ⁶ for hydrogen, methyl or ethyl,

R for hydrogen, methyl, ethyl, phenyl, through alkyl or alkoxy phenyl substituted with 1 to 2 carbon atoms or a phenyl radical ortho to the Ring B is condensed,

R for hydrogen, methyl or ethyl,

R represents methyl or phenyl and

has the same meaning as above

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··· η * ft * a

Nonionic substituents in the context of the present Invention to dispose of the substituents which are customary in dye chemistry and which do not dissociate under customary conditions of manufacture and use stand, such as halogen, e.g. fluorine, chlorine, bromine, hydroxy, alkyl, alkenyl, aryl, aralkyl, aryloxy, alkoxy or hydroxyalkoxy, Cycloalkoxy, aralkoxy, aryloxyalkoxy, alkylthio, aralkylthio, arylthio, nitro, cyano, formyl, alkylcarbonyl, Arylcarbonyloxy, alkylcarbonyloxy, alkoxycarbonyloxy, Alkylcarbonylamino, alkylaminocarbonyloxy, arylcarbonyl, aralkylcarbonyl, arylsulfonylamino, aralkylsulfonylamino, Alkylsulfonylamino, ureido, N-alkyl-ureido, Aryloxycarbonylamino, alkyloxycarbonylamino, carbamoyl, N-alkyl-carbamoyl, Ν, Ν-dialkyl-carbamoyl, N-alkyl-N-arylcarbamoyl, Sulfamoyl, N-alkyl-sulfamoyl, Ν, Ν-dialkylsulfamoyl, Alkylsulfonyl, alkenylsulfonyl, arylsulfonyl, Aralkylsulfonyl, aryloxysulfonyl, aryloxycarbonyl, alkoxycarbonyl, Aralkoxycarbonyl, mono-, di- or trialkylsulfamidine, Alkylarylsulfamidine, alkylcycloalkylsulfamidine and arylazo. Polyglycol ether residues with halogen, Hydroxy or alkyloxy substituents are suitable.

In the formulas and in the nonionic substituents mentioned above, alkyl radicals are to be understood as meaning in particular special C ₁ -C 6 -alkyl radicals and alkenyl radicals are to be understood in particular as C _{3 -C 5 -alkenyl radicals.}

Suitable aryl radicals are in particular the phenyl or naphthyl radical.

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Suitable aralkyl radicals are in particular the benzyl, VC or β-phenylethyl, OC, β or ) l -phenylpropyl radical. Cycloalkyl is preferably understood to mean cyclohexyl. By condensing further rings onto rings A and B, naphthalene, tetralin or benzdioxane systems, for example, are formed.

The aliphatic and isocyclic radicals can for their part contain the aforementioned nonionic substituents wear.

Acyl is understood to mean, for example, acetyl, propionyl, benzoyl or carbamoyl.

The advantage of the new process is that - without going through an aqueous phase, from which the Dyestuff can be isolated by salting out, filtering off and drying and without the dyestuff so isolated must be dissolved again to a spinning solution and then filtered - immediately to a usable one Spinning liquid setting arrives. With the new procedure There is therefore no waste water, and the labor and energy-intensive drying of the isolated from the solution There is no dye.

The dye solutions obtained are very high are concentrated in coloring salts of the formula (I), for example they contain 10 to 70% coloring matter.

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a ti η · * * * c «·

330102 / f

-Vl-

Suitable aldehydes of the formula (II) are, for example, 4-dimethylaminobenzaldehyde, 4-diethylaminobenzaldehyde, 4- / T2-chloroethyl) -methylaminoZ-benzaldehyde, 4- / T2-chloroethyl) -ethylaminoZ-benzaldehyde, 4- / butyl (2-chloroethyl) amine 7-benzaldehyde, 4- ^ butyl (2-cyanoethyI) amino? -Benzaldehyde, 3- / M4-formyl-phenyl) -methylamino7-propanenitrile, 4 - / "(2-chloroethyl) -ethyl-amino7-2-methyl-benzaldehyde, 4 - ^ "(2-cyanoethyl) -methyl-amino7-2-methyl-benzaldehyde, 4- £ N-ethyl-N-ß- (4-methoxycarbonylbenzoyloxy) -ethylamino) -2-methylbenzaldehyde, N-methyl-3-formylcarbazole, N-ethyl-3-formylcarbazole, 4- (benzyl-ethylamino) -benzaldehyde, 4- (benzyl-ethylamino) -2-methylbenzaldehyde, 4/4-ethoxyphenyl) -ethyl) -amine7-benzaldehyde, 4- ^ 74-ethoxyphenyl) methyl) amino7-benzaldehyde, 2-methyl-3-formyl-1H- ^ indole, 1-methyl-2-phenyl-3-formyl-indole, 1 ^ -dimethyl-S-formylindole.

Suitable compounds of the formula III are, for example • 1 ^, S-trimethyl ^ -methylene-indoline, 1,3, 3, 5-tetramethyl-2-methylene-indoline, 1,3,3-trimethyl-5-chloro-2-methylene indoline, 1,3,3-trimethyl-5-methoxy-2-methylene-indoline, 1, S ^ -trimethyl-S-carboethoxy-S-methylen-indoline, 1,3,3-trimethyl-5-methylsulfonyl-2-methylen-indoline, 1,3,3-trimethyl-5-benzyl-2-methylene-indoline, 1,3,3-trimethyl-5-benzoyloxy-2-methylene-indoline, 1,3,3-trimethyl-5- (4-chlorophenoxy) -2-methylene-indoline, 1,3,3-trimethyl-7-methoxy-2-methylene-indoline, 1,3, S-trimethyl-S-chloro-V-methoxy-2-methylene-indoline, 1,3,3-trimethyl-5,7-dimethoxy-2-methylene indoline, 1,3,3-trimethyl-7-phenoxy-2-methylene indoline ·

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- do-

Intermediate products of the formula IV which are suitable for the process are, for example: 1,3,3-trimethyl-2-methylene-indoline- ^ / -aldehyde, 1,3,3, S-tetramethyl ^ -methylene-indoline- LC aldehyde, 1, SiS-trimethyl-S-chloro ^ -methylene-indoline- Lu aldehyde, 1,3,3-trimethyl-5-methoxy-2-methylene-indoline- ^? -aldehyde, 1,3,3 ~ trimethyl-5-carboethoxy-2-methyleneindoline- LC -aldehyde, 1,3, S-trimethyl-S-methylsulfonyl-Z-methylen-indolinü? -aldehyde, 1,3,3- Trimethyl-5-benzyl-2-methylen-indoline- i / o -aldehyde, 1,3,3-trimethyl-5-benzyloxy-2-methylen-indoline- i \) -aldehyde, 1,3,3-trimethyl- 5- (4-chloro-phenoxy) -2-methylen-indolin-to -'-aldehyde, 1,3,3-trimethyl-7-methoxy-2-methylen-indoline-K? -aldehyde, 1,3, S-trimethyl-S-chloro-T-methoxy ^ -methylene-indoline- U? -aldehyde, 1,3,3-trimethyl-1-5,7-dimethoxy-2-methylene- indoline-Iv -aldehyde, 1,3,3-trimethyl-7-phenoxy-2-methylene-indoline- 10- aldehyde.

Suitable amines of the formula (V) are, for example: 4-amino-diphenyl ether, 4-amino-4'-methyl-diphenyl ether, 4-Amino-4'-ethy! -Diphenylether, 4-Amino-4'-tert.-butyl-diphenylether, 4-amino-4'-cyclohexyl-diphenyl ether, 4-amino-2'-methyl-diphenyl ether, 4-amino-3'-methyldiphenyl ether, 4-amino-4'-methoxy-diphenyl ether, 4-amino-3'-methoxy-diphenyl ether, 4-amino-4'-ethoxy-diphenyl ether, 4-amino-4'-acetylamino-diphenyl ether, 4-amino-4'-hydroxydiphenyl ether, 4-amino-4'-nitro-diphenyl ether, 4-amino-4'-chloro-diphenyl ether, 4-amino-2'-chlorodiphenyl ether, 4-amino-3'-chloro-diphenyl ether, 4-Amino-phenyl- OC-naphthylether, 4-aminophenyl-ß-naphthyl ether, 4-amino-2 ', 3', 5'-trimethy! -Diphenyl ether, 4-aminophenyl benzyl ether, 3-

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3 "30Ί02Α

- 1-3 -

Aminophenyl benzyl ether, 2-aminophenyl benzyl ether, 2-aminodiphenyl ether, 4-aminophenyl-4'-methylbenzyl ether, 4-aminophenyl-4'-chlorobenzyl ether, 4-aminophenyl-2'-chlorobenzyl ether, 4-aminophenyl-3 ', 4'-dichlorobenzyl ether, 4-aminobenzyl-2 ', 4', 5'-trichlorobenzyl ether, 3-aminophenyl-4'-methylbenzyl ether, 3-aminophenyl-4'-chlorobenzyl ether, 3-aminophenyl-2'-chlorobenzyl ether, 3-aminophenyl-3 ', 4'-dichlorobenzyl ether, 3-aminophenyl-2 ', 4', 5 '-trichlorobenzyl ether, 2-aminophenyl-4'-methylbenzyl ether, 2-aminophenyl-4'-chlorobenzyl ether, 2-aminophenyl-3 ', 4'-dichlorobenzyl ether, 2-aminophenyl-2 ', 4', 5'-trichlorobenzyl ether, 4-amino-2-methylphenyl-benzyl ether, 5-amino-2-methyl-phenyl-benzyl ether, 2-amino-5-methyl-phenyl-benzyl ether, 4-Amino-2-methoxy-phenyl-benzyl ether, 4-amino-3-methoxy-phenyl-benzyl ether 4-amino-3-methyl-phenylbenzyl ether, 4-Amino-3-chloro-phenyl-benzyl ether, 4-Amino-2-chloro-phenyl-benzyl ether, 4-amino-2-methyl-phenyl-4'-methylbenzyl ether, 5-Amino-2-methyl-phenyl-3 ', 4'-dichlorobenzyl ether , 2-amino-5-methyl-phenyl-4'-chlorobenzyl ether, 4-amino-2-methoxyphenyl-4'-methylbenzyl ether, 4-Amino-3-methyl-phenyl-2 ', 4', 5'-trichlorobenzyl ether, Aniline, p-toluidine, m-toluidine, o-anisidine, m-anisidine, p-anisidine, o-phenetidine, p-phenetidine, 4-dodecyloxyaniline, 4-amino-acetanilide, N-benzoyl-p-phenylenediamine, 2,4-dimethoxy-aniline, 2,5-dimethoxy-aniline, 3,4-dimethoxy-aniline, 2-chloro-4-amino-anisole, 2,4,5-trimethylaniline, 2,3,5-trimethyl-aniline, 5-amino-2-acetylaminoanisole, 6-amino-3-methoxy-toluene, 3,4-dicyano-aniline, p-sulfanilic acid amide, 4-amino-benzamide, 4-chloro-aniline,

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-VA-

4-fluoro-aniline / 1,2,3,4-tetrahydro-5-amino-naphthalene, 4-amino-2,5-diethoxy-benzoic anilide, 4-amino-2-methy1-5-methoxy-benzanilide, 4- Cyclohexyl aniline, 2,4-diethoxyaniline, 1-amino-naphthalene, 2-methyl-2 _# 3-dihydro-indole, hexahydrocarbazole, 2,3,3-trimethyl-2,3-dihydro-indole, 2,3, 3-trimethyl-5-methoxy-2,3-dihydro-indole, 4-aminobrenzcatecholethylene ether, 6-amino-benzdioxane, 1,2,3,4-tetrahydro-6-methoxy-quinoline, 4-methylamino-phenylbenzyl ether, 4- Ethylamino-phenylbenzyl ether.

Suitable acids of the formulas (VI) and (VII) are, for example: benzenesulfonic acid, 2-methylbenzenesulfonic acid, 4-methylbenzenesulfonic acid, 2,4-dimethylbenzenesulfonic acid, 2-chloro-benzenesulphonic acid, 4-chloro-benzenesulphonic acid, 2,4-dichlorobenzenesulfonic acid, 4-hydroxybenzenesulfonic acid, 4-methoxybenzenesulfonic acid, naphthalene-1-sulfonic acid, Naphthalene-2-sulfonic acid, methanesulfonic acid, Ethanesulfonic acid, butanesulfonic acid, methylsulfuric acid, Ethylsulfuric acid or mixtures thereof and • phosphoric acid diethy! Ester.

According to the claim, the dyes are prepared by either first adding the solvent one after the other Aldehyde, then the organic acid and finally the base or the base and acid are introduced and then adding the aldehyde.

The reaction temperature is chosen in the range between 20 ⁰ C and 100 ⁰ C, preferably between 3O ⁰ C and 60 ⁰ C.

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330102A

The molar ratio of aldehyde / base is preferably 1, whereas, based on this, the ratio of organic acid is 1 to 2 Equivalents are used. The total concentration based on the solvent can be between 10% and 70%.

The implementation is surprisingly smooth and quantitative. In this way, stable, concentrated, minerals are obtained salt-free solutions of dyes that can be added directly to the spinning system.

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example 1

44.4 g of p-dimethylaminobenzaldehyde and 90 g of p-toluenesulphonic acid are introduced successively into 450 g of dimethylformamide and heated ^{to 50 ° C. with stirring.} In the resulting solution added dropwise to stirred and allowed 10 'hours at 5O ⁰ C 51 g of 1,3,3 ~ 2-methylene-indoline-trimethyl within 15 minutes.

After cooling to room temperature, the ready-to-use violet dye solution is made with about 280 g of dimethylformamide set.

The solution contains the dye in a concentration of approx. 20%

CH

XH = CH- <
CH ₀ V ^ = / \,

and dyes - added to the spinning solution - polyacrylonitrile in bluish red tones.

Example 2

66.5 g of 2-methyl-indoline and 100 g of p-toluenesulfonic acid are stirred in 1245 g of dimethylformamide. At 35 ⁰ C slowly 101 g of Fischer's aldehyde / Ti, 3,3-trimethyl-indoline-

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-Yl-

2-ylidene) acetaldehyde / registered. After 2 hours at 35 ^° C., the reaction is complete. After cooling to room temperature, the yellow spinning dye solution is adjusted to the desired color strength with dimethylformamide.

The solution contains the dye of the formula

^N '^ CH = CH-N.
CH-,

-CH.

CH ₃
and dyes polyacrylonitrile in orange tones in the spinning solution.

The following are examples of the dye solutions that can be prepared using the processes outlined:

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is -

CH.

violet

CH

CH-

CH,

yellow

^CH 3

in dimethylformamide (analogous to example 1)

CH = CH

CH.

Red

in diniethylacetamide (analogous to example 2)

in dimethylformamide (analogous to example 1)

violet

in dimethylforraamide (analogous to example 1)

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orange

in dimethylacetanide (analogous to example 1)

'greenish yellow

CE ₃ SO ₃

in dimethylformamide (analogous to example 2)

OCH,

greenish yellow

CH ₃ SO ₃ ^,

in dimethylformamide (analogous to example 2)

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Claims (9)

Claims 1. Process for the preparation of solutions of cationic Methine dyes by condensation of aromatic isocyclic or heterocyclic or araliphatic Aldehydes and compounds containing methylene or amino groups, characterized in that that the condensation in an organic solvent suitable for spin dyeing in Carries out the presence of a sulfonic or phosphonic acid . 2. The method according to claim 1 for the preparation of solutions of dyes of the general formula A-CH = CH - (- N -) - B ι "I R (D worm for 0 or 1, A stands for an isocyclic or heterocyclic aromatic radical or a radical of the formula Le A 22 087 «W . for alkyl, alkenyl or aralkyl, B for an isocyclic or heterocyclic aromatic radical or a radical of the formula CH. R for hydrogen / alkyl or aralkyl or for Alkylene, the one with B in the o-position to the nitrogen connected is, X for an anion of the formula Y SO ₃ ⁽ ~ ^ or / ^P0 2 ⁽ " ^{) and} Y is alkyl, aryl or alkoxy stand in which A or B carries a positive charge, and in which a, A, B, R, R ₁ , R ₂ and Y can be substituted by nonionic radicals, characterized in that the condensation of aldehydes of the formula A-CHO with compounds of the formula Le A 22 087 b- or of aldehydes of the formula CH. with amines of the formula NH-B in the presence of acids of the formula 330102Α Y SO ₃ H or carried out in organic solvent. 3. The method according to claim 1 for the preparation of solutions of dyes of the general formulas CH., -CH. ?, XIH = CH-N- (R ⁴ ). YSO Le A 22 087 «« «% · VW« I and YSO. worm R for hydrogen, an alkyl radical with 1 to 4 carbon atoms, halogen, alkoxy with 1 to 4 carbon atoms, phenoxy, benzyloxy, benzyl, carboxyl, phenoxyethyl, phenoxyethoxy, an alkyl carboxylate with 1 to 4 carbon atoms, one optionally through Carbonamide group substituted with 1 or 2 C ₁ to C ₄ alkyl radicals, a sulfonamide group optionally substituted by 1 or 2 C ₁ to C alkyl radicals, alkylsulfonyl with 1 to 4 carbon atoms, phenylsulfonyl, cyano, trifluoromethyl, acetyl - or benzoyl group, Le A 22 087 R represents an alkyl radical with 1 to 4 carbon atoms which is optionally substituted by hydroxy, alkoxy, acyloxy, halogen, cyano, carboxy, C _{1 - to C - carbalkoxy, carbonamido or acetyl,} 2 R has the same meaning as R or together with the benzene ring B a tetralin-, naphtha1in- ■ or benzdioxane ring system, R represents hydrogen or an alkyl substituent that has a 5- or 6-membered ring to the adjacent Position of the aryl ring B closes where in this case formed heterocyclic 5- or 6-membered ring, optionally alkyl-substituted or can be condensed with another carbocyclic ring, R stands for hydrogen or a radical with the same Meaning like R, R can have the same meaning as R, or optionally by alkyl or alkoxy with 1 to 4 carbon atoms substituted phenyl, or an alkyl substituent which has one 5- or 6-membered ring to the adjacent position of the aryl ring B closes, this heterocyclic 5- or 6-membered ring formed thereby, optionally alkyl-substituted or with or with another carbocyclic Ring can be condensed, stands, Le A 22 087 - * s- 330102A R ⁸ for hydrogen, C. to C ₄ -alkyl, R represents hydrogen, C- to C ₄ -alkyl _f phenyl optionally substituted by alkyl having 1 to 4 carbon atoms, 'Y has the meaning given in claim 2 and η and ρ are 1 or 2. 4. The method according to claim 1 for the preparation of solutions of dyes of the formulas of claim 3, in which η and ρ stand for 1, R for hydrogen, chlorine, methyl, methoxy, Ethoxy, benzyl, phenoxy, benzyloxy or carbomethoxy, R ³ for methyl, R for hydrogen, methyl, methoxy, ethoxy, Benzyl, benzyloxy, phenoxy, chlorine, C-- bis C 1-4 alkyl substituted carbonamide or together with ring B for a naphthalene, tetrahydronaphthalene or benzdioxane ring system, Le A 22 087 - 2-6 - R for hydrogen or preferably for an alkyl radical which closes a 5- or 6-ring to the o-position of ring B, which _{can be substituted by 1 to 3 C 1} -C 6 -alkyl groups or condensed with a cyclohexane ring, stand, R for hydrogen, methyl or ethyl, R represents hydrogen, methyl, ethyl, phenyl, substituted by alkyl or alkoxy having 1 to 2 carbon atoms Phenyl or a phenyl radical, the is condensed ortho to ring B, R stands for hydrogen, methyl or ethyl and 9
R represents methyl or phenyl. 5. The method according to claim 1, characterized in that the condensation is carried out in the presence of the acids of the formulas of claim 2 carries out ^ in which Y for an alkoxy radical with 1 to 4 carbon atoms, one optionally with 1 to 3 alkyl radicals with 1 to 4 carbon atoms, alkoxy radicals with 1 to C atoms, halogen or hydroxyl substituted Phenyl radical or a C- to C-alkyl radical stands. Le A 22 087 6. The method according to claim 1, characterized in that the condensation in amides of lower aliphatic Carboxylic acids performs. 7. The method according to claim 1, characterized in that the condensation in dimethylformamide ,, diethylformamide or dimethylacetamide. 8. Use of the solutions prepared according to claim 1 for the dyeing of acidic modified Synthetic fibers. Le A 22 087